Process for the preparation of an aluminum chloride catalyst



SPt 15 1942- s. B. THoMfAs ET AL 2,295,977

PROCESS FOR THE PREPVRATION 0F AN ALUMINUM CHLORIDE CATALYST Filed Sept. 28, 1939 `Inwzntors Somud cnson Thomas Frank MoHhewMcMHon Patented Sept. A1.5, 1942' s PATENT oFFlcE- rRocEss Fou' THE PREPARATION or AN jALUMINUM cuLomDn cATALYsfrl Samuel Benson Thomas and Frank Matthew Mc- .Millam Berkeley, Calif., asslgnors to Shell Development Company, San Francisco, Calif., a

corporation of Delaware i `Application September 28, 1939, Serial No. 296,898

UNITEo STATE class of catalytic agents.

, proved catalysts comprising aluminum `halides and' to a process and apparatus for their preparation.

The aluminum halides constitute a well-known These catalysts,

especially aluminum chloride and aluminum.

bromide, are capable of catalyzing a .large number` of reactions and find considerable applicato provide methods and apparatus for the practical preparation of said catalysts. i

It has recently been found that catalytic materials having superior properties are obtained by combining anhydrous aluminum halides, and

especially aluminum chloride, with Isuitable carrier or supporting materials in a particular manner. These catalysts are described in copending application No. 290,256 tiled August 15, 1939.

tion in the alkylation of isoparaflns with ole- 10 Accrding to the DIOCGSS Of Said COD'eIldn apns, the isomerization of saturated hydrocarbons, 'PliCaOm a mixture 0f aluminum halide and a the polymerization of olefinic hydrocarbons, the Suitable atalyst Carrier iS heated While under cracking of hydrocarbons, the FriedelCraft re- SupelatmOSDherC' Pressure at a temperature actions, and the like. vIn many reactions using sufficiently high t melt the aluminum halide. these catalysts, a large surface is not essential l 'and the catalytic mass'obtained upon cooling since the aluminum halides are soluble to a cerv iSbrOken 11p into fragments of the desired size. tain `extent in many of the. liquid reaction mx- Theatalysts plupaed by this Simple procedure tures and in such cases they do not act entirely are Quite different than-Vibe SUDDOlted catalysts as heterogeneous catalysts. In most cases the prepared by the Older methods and DOSSESS aluminum halide is simply' suspended-in the re- 2o valuable and unexpected properties. One of the action mixture, preferably with stirring. In a advantageus properties 0f these catalysts, is few cases, especially when executing the reactheir increased catalytic activity. This increased tion in the-vapor phage, the aluminum halide is activity is pronounced in some cases and less so employed in combination with carrier or Supin others and depends Primarily 'upon the par'. porting materials, Such as pumice, activated ticular material with which the aluminum halide charcoal, and the like. The function of the 1S COmbned- Since these CatlYStS are. in gencarrier material in these cases is primarily to eral more active than catalysts 0f the Same prevent the aluminum hande from agglomeretcomposition prepared by conventional methods, ing to a hard lump in liquid phase processes and it is-apparent that the increased activity is due s to produce a, catalyst having s fixed physical to a promoting eiect wh1ch is materially enshape better adapted for vapor phase reactions. harmed by the method of preparauon: These supported catalysts are usually prepared We have nowfound that the Promotmg actlon by simply mixing pieces of carrier material with of Various ca rner and supportmg mammals is the ne powdered` anhydrous aluminum hande further materially enhanced and that even'nmore whereupon the surface of the carrier material deslrable catalyst .are prodllced by Combming becomes covered with the powdered aluminum h alnrfdrl aluglilnlalggf ca e a 1 s i a hande' @other method for produclng support' to the process ofthe present invention superior ed aluminum halide catalysts, wh1ch has the advantage of allowing the aluminum halide concatalysts are. prepare? by spakng pieces of a' tent to be varied Overa Wide range, is te press 40 'suitable carrier material havmg the desired size, Y porosity, mechanical strength, etc., in a bath of of mold suitable mxures conpmmg the de molten anhydrous aluminum halide, draining siredfamount of alummum .hahdef off the jexcess aluminum halide and cooling, all

An object of the present 1nvent1on 1s to'prowhile under smseratmosrmericl pressure. Wd? new and Improved prqmoted alummum In order to prepare the present improved catahallde catalysts havlng exceptionally high catalysts apparatus embodying the principles of the lYtlC aCtlVlty Another Oblct 0f the mVen'lOn apparatus illustrated in the attached drawing' is to provide aluminum halide catalysts which, may advantageously be emp1oyed i ,When employed m Vapol Phuse'reuctlon ut ele Figure I of the attached drawing shows a Vated. teulperatules. mullltam their actlvlty for cross-section in' elevation of`one Verysimple type long periods of time with exceptlonally low loss of suitable apparatus. Referring to Figure I, of aluminum halide by volatilizatlon. Still anis a pressure vessel provided with a removable other object is to providepromoted aluminum `cover 2` which is preferably provided with a halide catalysts having very high mechanical valved connection 4. A basket or cage 5 having strength. Other objects of 'the invention are a removable top 8 is supported in the vessel by means of a shaft Gpassing through a packing gland 1 in the cover. The basket or cage is so adapted as to be adjustable vertically in the vessel while under pressure. The vessel and basket are so proportioned that when the` basket is 5 raised to its uppermost position, the vessel is capableof containing sulcient fused aluminum halide below the basket to completely cover the latter when the same, filled with pieces of carrier material, is lowered to its lowermost position (as shown).

In the' claims the expression a substantial excess of molten aluminum chloride is to be readto mean a quantity ofl aluminum chloride in excess of that adsorbable in the carrier vand suiiicient to cover the carrier when it is immersed therein.

The preparation of the present catalysts using apparatus of this type'is simple. A sufficient quantity of anhydrous aluminum halide (preferably aluminum chloride) is charged into the pressure vessel; the basket is filled with pieces of carrier material of the desired size and drawn up clo'se to the cover; and the cover is secured. After introducing a gas to give an increased pressure, if desired, the apparatus is heated by any suitable means, such as by immersing in a hot oil bath 3. As soon as the aluminum halide isy fused, or any time thereafter, the basket is forced down into the melt. After allowing the carrier material to remain in the molten alumi- Anum halide for a few minutes or longer, the

basket is raised to its uppermost position and the catalyst allowed to drain. When the excess aluminum halide has drained-sumciently from the catalyst particles, the apparatus is cooled, the pressure released, and the catalyst/removed.

While apparatus such as illustrated in Figure I is quite suitable for the production of smaller quantities of catalyst, larger quantities are more conveniently and leconomically prepared ln apparatus such as illustrated in Figures II and III.

The apparatusI illustrated in Figure II comprises two pressure vessels I and I| interconnected in their upper and lower portions by pipes I5 and` I6. The vessels are provided with suitable heating and/or cooling means, such as jackets I2 and I3, for the circulation of suitable media. Vessel il is provided witha removable basket or cage I4 for the catalyst.l

The solid anhydrous aluminum halide is charged to, vessel I0 and the carrier material is charged into the basket Il in vessel Il. The aluminum halide is fused by heating vessel l0 and the melt conveyed to vessel via pipe I6. In order to keep the melt from freezing in vessel I"l and/or in pipe I6 during the impregnation and transfer, these may be heated by circulating a suitable heated medium through the jackets i3 and I8.. After the carrier material is impregnated with the molten aluminum halide, valve |`I is closed, and the pressures in the two vessels are adjusted to force themolten aluminum halide back into the vessel 40 viaI pipe I6. Thus; if necessary, a gas may be forced into vessel II via a valved connectionfl, and/or gas may be al- `lowed to escape from vessel In via a valved connection 20. When the level of the molten aluminum halide is below the basket in Vessel Il, a,v cooling medium may be circulated in jacket I to freezev the aluminum halide in pipe I6. After the catalyst has had time to drain, the vessel II is cooled to below the melting point of the aluminum halide, any residual pressure isreleased via connection I9, and the catalyst is removed,

The process is repeated by charging a fresh quantity of carrier material, heating pipe I6 to melt the aluminum halide plug, heating vessel |I, and continuing as described above.

Another apparatus which may advantageously be employed for the preparation of large quantities of catalyst is illustrated in Figure III. The apparatus illustrated in Figure III comprises a still 30 communicating overhead and below with a catalyst chamber 3|. The carrier material to be impregnated is charged into chamber3| via a closable opening 32. The carrier material in chamber 3| rests upon a false bottom 33 and is capped by a false top 34 so adapted as to be put in place after the carrier material has been charged.

In order to impregnate the carrier material with molten aluminum halide, the lower connecting pipe 35 is cooled, for instance by passing a cooling medium through a jacket 39, and aluminum halide is distilled from still 30 until the chamber 3| is filled with liquid condensate. After the carrier material is sufficiently soaked in molten aluminum halide, pipe 35 is heated to melt the plug of aluminum halide therein, and the catalyst is allowed to drain. When the catalyst has drained suillciently, chamber 3| is cooled 'to below the melting point of the aluminum halide and the catalyst removed through a manhole 38. The pressure in the system may be regulated by the addition and withdrawal of gas via a valved connection 31 situated above the catalyst bed.

In the apparatus illustrated in Figures II and III, the opening and closing of the lower pipes I6 and 35 is effected by freezing and melting the aluminum halide therein. In the handling of molten aluminumhalides, this is a most advantageous device. If desired, however, suitable valves may be used. f

Of the various common catalyst carriers or supports which may be combined with the aluminum halldes, according to the present invention, the various siliceous and/or aluminous materials of natural or synthetic origin which may contain an appreciable. amount vof firmly bound or strongly adsorbed water, are preferred. While we do not desire our invention to be limited to the .soundness or accuracy of any theories advanced to explain the advantageous results, it

appears that the promoting action of these carrier materials is somehow'connected with their firmly-bound water. Suitable `materials of this category are, for example, the natural-occurring minerals and clays, such as bauxite, dawsonite, gibbsite, Florida earth, bentonite, kaolin, pipe clay, meerschaum, montmorillonite, the permutites, diatomaceous earth, kieselguhr, infusorial earth, and the like;y the various treated clays and clay-like materials, such as Tonsil, Celite, Sil-O-Cel, Terrana, and the like; and artificially prepared materials such as Activated Alumina, the artificial permutites, and the like. These materials are preferably but not necessarily, partiallyl dehydrated by heating in-a dry atmosphere at a.temperature somewhat higher than that at which they are to be employed, for instance, at about 200 C. to 400 C.. until they substantially cease to give olf water. Of these materials and similar materials of this category activated alumina andv the diatomaceous earths, such as Sil-O-Cel, are found to be particularly effective. Particularly effective combination catalysts with "activated alumina are described and claimed in copending application No. 292,295, filed August 28, 1939.

Although materials of the above class, in general,` produce ythe most active catalysts,any of the present catalysts, may or may not exert a promoting` action upon the catalytic activity. of the aluminum halide,v are' preferably employed in the form of pieces, fragments, pills, macaronis, or the like, of size and shape suitable'for use in catalytic reactions. Since, in the present method ofpreparation, the excess aluminum halide is allowed'to drain from the catalyst prior to cooling below the melting point of the aluminum h'alide, the resulting catalyst is ofthe' same shape, size and nearly of the same appearance as the original carrier material employed. In such cases when it'is desired to employ a carrier which is toofragile or occurs naturally in too flne a state of subdivision, it may be pilled or briquetted with or without binding material into suitably shaped pieces prior to treating with the molten aluminum halide.

lThe present process is applicablevfor the preparation of catalysts using the anhydrous aluminum halides. While catalysts containing other aluminum halidesmay be prepared and are suitable, those prepared with aluminum chloride are by far the most useful and practical. For the preparation of aluminum chloride catalysts, any substantially anhydrous aluminum chloride, such as the powdered commercial product, .may be used. For some hydrocarbon reactions, especially atelevated temperatures, it is found that catalysts prepared from aluminum chloride containing an appreciable quantity of iron chloride are much inferior. The deleterious eiect of the iron about two hours and thoroughly draining, cataor higher may, of course, be employed, but require more expensive equipment. In order to bring the pressure within the .preferred range, the vapor pressure of the aluminum halide may 1 be supplemented by a gas, such as air, N2, CO2,

Hz, HC1, or the like.

In order to realize the maximum promoting action of the carrier material, (when promoting carrier materials are employed) the carrier material shouldfbe submersedn an vexcess of the molten aluminum halide and the excess aluminum halide allowed to drain off.` This procedure,

we have found, automatically produces a cata,

lyst with a suitable aluminum halide content. The percentage of aluminum halide in thepresent catalysts, however, depends upon the carrier material employed, and somewhat upon the length of time allowed for impregnation, the length of time allowed for draining, the temperature during the impregnation and draining, and the viscosity of the aluminum halide melt. For example, when'impregnated at about 225 C. for

lysts prepared with the following carrier materials were found to contain the following percentages by weight of aluminum chloride.

Per cent (about) Activated alumina `30 Sil-O-Cel (a diatomaceous earth) 33 Pumice 40 Silica gel 23 Bauxite 39 Majolica chips 11 Catalystsprepared with very porous carriers and aluminum chloride at about 200 C. may contain, for example, as much as about aluminum chloride.

may be overcome and excellent catalysts pre-` pared from aluminum" chloride `contaminated with iron chloride by adding a small amount of metallic aluminum to the aluminum chloride. The amount .of aluminum required depends upon the amount of iron present and is usually quite small, for example 1% or less of the metal, preferably employed in a finely divided state, usually also advantageous lto employ corrosion resistant or aluminum-lined apparatus in the catalyst preparation.

The temperature at whichv the impregnation I and subsequent draining of the catalyst takes C. and below Vthe boiling point of the aluminum chloride under the prevailing pressure, and is conveniently between about 200 C. and about The impregnation of the carrier material'v and thesubsequent draining are executed under a `suiiices, but larger amounts may be used; It is superatmospheric pressure, preferably at least to about so ibs./in.2 pressures if-1000 iba/in.2

materiaL is, of course, not excluded.)

whereas in the promoted'catalysts disclosed in` theabove-mentioned copending application, the

Both the catalysts and the methodA of preparation of the present invention have several distinct advantages. One of vthe advantageous characteristics of thecatalysts is their increased catalytic activity. This increased catalytic activity'is Very pronounced in some cases and less so in others and depends primarily upon the particular material with which thealuminum halide is combined. Since they are, in general, more effective than catalysts of the same composition prepared by conventional methods and by the method of copending vapplication No. 290,256,

flied August 15, A1939 it is apparent thatI the increased activity is due to apromoting effect of the carrier material which is enhanced by the present method of preparation. The more per-v fect utilization of the promoting effect of the various above-described mineral carrier materials is believed to be due toa more perfect saturation of all of the available surface of the carrier material with the optimum amount of fused aluminum halide. (The possibility of a small amount of chemical interaction between the molten aluminum halide and the mineralccarrier surface of the carrier is thickly coated with aluminum chloride and suilicient excess aluminum chloride is present to bond the material, the carrier particles in the catalysts prepared according to the present invention are found to have their surfaces completely covered with a very thin film of fused aluminum halide which appears to be just suicient to produce the most eilicient catalyst.

The remarkable catalytic activity of an Thus,

activated alumina.aluminum chloride cata.- lyst prepared according to the present process is illustrated in the following example:

Example I Normal butane and isobutane were each passed separately over an "activated alumina"alumi num chloride catalyst prepared as described in Example II and containing 30% aluminum chloride. The conditions were the same as those described in Example II. The results were as Example I clearly shows that even under these more or less unfavorable conditions the reaction has essentially reached equilibrium. These results are not obtained with conventional catalysts even when employing' much higher temperatures and pressures.

Another advantageous characteristic of the present catalysts is their high mechanical strength. Due to the superior strength of most of the present catalysts, they can be used in larger, more economically employed beds'. They also suffer much less disintegration during use and, consequently, can be used for much longer periods of time before the efficiency of the bed becomes impaired by channeling, etc. due to disintegration.

Still another important characteristic of aluminumA halide catalysts prepared according to the present method is their 4ability to retain the aluminum chloride when employed at high temperatures. When employed at high temperatures the present soaked and drained catalysts losevery little aluminum halide by volatilization.

Although the present catalysts may be advantageously employed in v'any capacity wherein aluminum halide catalysts have hitherto been employed, they are exceptionally effective and advantageous in promoting hydrocarbon reactions such,l in particular, as .isomerization, alkylation, and polymerization. The effectiveness of the present catalysts in isomerization is illustrated, for instance, in the following examples:

Example yII Pieces of activated alumina of 6 to 8 mesh i were soaked in an excess of molten anhydrous aluminum chloride under pressure in an apparatus similar to that illustrated in Figure I of the attached drawing. After soaking for about two f' Temperature 100 C.

v Pressure.. 11 atmospheres. Space velocity 6 mol/liter/hr. .Hydrogen chloride present 2 mol Cil reaction products normally present was unusually small. ,y

Example III A catalyst prepared as above-described and containing 25.7% aluminum chloride was used fo'r the isomerization of normal butane to iso,- butane under the following conditions:

Temperature 10S-110 C. Pressure 12 atmospheres. Amount of catalyst 6.1 kgs.=5.'7 liters. Amount of hydrogen chloride in feed 2.3 mol @/0. Feed rate in kgs. N-butane/liter catalyst/hr 0.32.

In 553 hours of continuous operation a total of 520 kgs. of isobutane (304. kgs. of isobutane per kg. of aluminum chloride) was produced at an average-conversion of 47%. The catalyst at the end of 553 hours of operation was Substantially unchanged in appearance and still active.

The present catalysts, as can be seen from the examples, not only possess outstanding activity, but retain their activity for long periods of time` When, after a long period of use, the catalytic activity nally becomes too low for economical use, the carrier may be recovered and reused, or

in some cases the catalyst may be regenerated.

Thus, for example, the degenerated catalyst may be treated witha suitable solvent, such as water, aqueous acid, aqueous solutions of ketones, isopropyl ether, etc. to remove the aluminum halide and impurities. The recovered carrier may then be recombined with fresh aluminum halide.

The present process for the preparation of the catalyst also has certain advantages aside from the quality of the catalysts. Thus, for example, the mixing of the aluminum halide and the carrier prior to heating, which should be done in a dry atmosphere, is entirely avoided; also, there are no ilnes from crushing and grading-operations to be reworked.

We claim as our invention:

l. Al process for the preparation of improved aluminum chloride catalysts especially suitable for catalyzing hydrocarbon reactions, which comprises the steps of soaking pieces of alumina in activated form, prepared by partial dehydration at a temperature above about 200 C. of crystalline alpha alumina trihydrate precipitated from a solution of sodium aluminate, in a substantial excess of molten anhydrous aluminum chloride over that inherently adsorbable in said alumina, said soaking being effected under pressure, draining ol excess molten aluminum chloride in an atmosphere containing aluminum chloride vapors under pressure, and cooling to below 190 C.

2. A process for the preparation of improved aluminum chloride catalysts especially suitable for catalyzing hydrocarbon reactions, which comprises the steps of soaking pieces of alumina containing firmly bound water and prepared by par- During 126 hours of continuous operation the averageisobutane content of the product was 60%. Furthermore, in proportion to the amount of isomerizatlon obtained, the 'amount of the side 75 tial dehydration at a temperature above about 200 C., said soaking being eected under pressure in a substantial excess of molten anhydrous aluminum chloride over that inherently adsorbable in said alumina, draining oi excess molten aluminum chloride in an atmosphere containing aluminum chloride vapors under pressure, and coolingv to below C.

3. A process for the preparation of improved aluminum chloride' catalysts especially suitable for catalyzing hydrocarbon reactions,rwhich comprises the steps of soaking pieces of diatomaceous earth containing rmly boundwater and prepared by partial dehydration at a temperature above about 200 C., said soaking being effected under pressure in a substantial` excess of molten anhydrous aluminum chloride over that inherently advsorbable in said diatomaceous earthLdraining off excess molten aluminum chloride in an atmos- 4 phere containing aluminum chloride vapors under pressure, and cooling to below 190 C.

4. A process for the preparation of improved aluminum chloride catalysts especially suitable for catalyzing hydrocarbon reactions,.which comprises the steps of soaking pieces of a mineral catalyst carrier containing firmly bound water and prepared by partial dehydration ata temi perature above about 200 C., lsaid soaking being effected under a pressure greater than 40 pounds per square inch in a substantial excess of molten anhydrous aluminum chloride over that inherently adsorbable in said carrier, draining oi excessmolten aluminum chloride in an atmosphere con-v taining aluminum chloride vapors under pressure,

l0 and cooling to. below 190 C.

SAMUEL BENSON THOMAS. l FRANK MATTI-IEW MCMILLAN, 

